Anthraquinone dyestuffs



ANTHRAQUINONE DYESTUFFS Milton L. Hoefle, Grosse Pointe Woods, Mich assignor to General Aniline & Film (Zorporation, New York, N.Y., a corporation of Delaware No Drawing. Original application Aug. 4, 1954, Ser. No. 447,886, now Patent No. 2,768,183, dated Oct. 23, 1958. Divided and this application Feb. 17, 1956, Ser. No. 566,073

11 Claims. (Cl. 8-25) This invention relates to the production of a new series of anthraquinone dyestuffs and to mixtures of such dyestuffs with other anthraquinone dyestuffs.

The problem of providing acid gas resistant dyestuffs in the blue range for cellulose acetate rayonfibers and other fibrous material having a basis of polymeric material has long been recognized. Dyestuifs of the amino anthraquinone series have up to the present time found wide-spread acceptance for such use, but in almost all instances, the blue colorations heretofore obtained do not have perfect resistance to acid gas fumes, the action of which in general produces reddening and dulling of the shade to an undesirable extent. While reddish-blue shades may per se be acceptable and even desirable in some instances, such shades are in general associated in the consumers mind with undesirable fading.

It is an object of this invention to provide a dyestuif composition capable of dyeing acetate rayon and other cfilm and fibrous materials in blue shades having substantially no tendency to fade to reddish tinges upon exposure to acid .gas fumes and other deleterious influences. Another object of this invention is to provide a new series of anthraquinone dyestuffs which maybeeinp loyed for producing such dyestuif mirrtures. Other objects and advantages of this invention will appear from the following description.

The attainment of the abov obects is mad ss'bl e I epo 1 e y s-trated above except for a carboxylic acid halide or ester the present invention which broadly comprises the provision of a composition comprising a blue anthraquinone dyestuif subject to changing to reddish hues upon exnosure to acid gas fumes and a blue anthraquinone dyesunl subject to changing to greenish hues upon exposure to acid gas fumes. In this manner, the reddish hues are counterbalanced by the greenish hues acquired by: the components of the composition upon exposure to acid gas fumes, whereby the original blue shade of the dyeings remain unaltered, though a dulling may in some instances be discernible. ,7 As -a further features of this invention, anew seriesfof amino anthraquinone dyestuffs have been found which possess the desirable property of producing blue shades in dyeings, which shades acquire greenish hues upon errposure to acid gas fumes. This new series of dyestuffs comprise compounds having the following formula:

" States Patent 2 the term lower alkyl includes such radicals as methyl, ethyl, propyl, isopropyl, and the like. It will be understood that in any particular compound included within the scop'e'of the above depicted formula, the defined sub stituents in the 1, 2 and 4-positions may have the same or different values within the ranges stated.

The compounds of the above formula may be madeby several difierent methods. In the following description of such methods, Y, R, X and n have the values given above. i I. aminoanthraquinone having a formula as illustrated above except for (a halide or sulfonic acid group in the 2-position is reacted with respectively CuCN or a water-soluble salt of hydrocyanic acid such as sodium cyanide, potassium cyanide, ammonium cyanide, etc, to replace the halide or sulfonic acid radical with a nitrile radical. Depending upon the starting components and the operating conditions, the resulting products may include compounds containing a nitrile group in the 3- position also.

II. An aminoanthraquinone having a formula as illustrated-above except for a reactive radical such as halide (C1 or Br), N0 alkoxy or aryloxy in the 4-position is reacted with an arylamine of the formula:

group in the 2position is reacted with an amine of the formula H N--(RO),,X to produce the corresponding carboxamide.

V. An aminoanthnaquinone having a formula as illustrated above except for a nitro groupiin the l-pos ition is subjected to reduction, followed if desired by reaction with a compound containing the group -(R0),,X'idined fo a reactive radical. I

An aniinoanthraquinone having a formula as illustrated above containing a nitrile group in 2-position is subjected to controlled hydrolysis (in view of the second ary amino groups present in 1 and 4-position) to produce the corresponding carboxamide, followed if desired by reaction with a compound having the group -(RO) X joined to a reactive radical.

Other methods of producing the compounds of this invention will become apparent to the person skilled in.

the art. Similarly, it will be obvious that in certain instancessensitive radicalsor groups already present in the intermediates from which the compounds of this invent-ion are produced must be blocked or protected during the reaction. p I v Besides the property of acquiring a greenish hue upon exposure mead 'gas'fumes, the above described compoundsof this invention have good lightand wash-fastness properties and good substantivity for the material to' colored. In addition to cellulose acetate, the *dyes't'ulffshf invention may be employed for coloring other natural or synthetic polymeric material in bulk, miner fiber form, including polyamides, polyesters, and" polyacrylonitriles and the like, such as nylon, Orlon, Dacron, Acrilan, Dynel, and the like.

The aforementioned compounds may be mixed in any required proportions with known blue anthraquinone dyestuffs subject to changing to reddish hues. upon exposure to acid gas fumes. The proportions of the compounds of this invention to be employed in such mixtures will of course be dependent upon the quantum of reddish hues to be neutralized or compensated for, which in turn is dependent upon the number, types and amounts of anthraquinone dyestufiis in the mixture producing such reddish hues, the material being dyed and the like. In general, blue anthraquinone dyestufi mixtures containing proportions of about 25 to 75 parts by weight of the compounds of this invention and about 75 to" 25 parts by weight of at least one other anthraquinone dyestuff subject to changing to reddish hues upon exposure to acid gas fumes will produce satisfactory blue shades which are substantially unaffected by exposure to acid gas fumes.

The following examples in which parts are by weight unless otherwise indicated, will serve to illustrate the invention, but they are not intended to limit it thereto.

Example 1 Into a stirred autoclave were placed 20.0 parts 1- amino-4-(oc-hydroxy-6-methoxy-m-toluidino) 2 anthraquinonesulfonic acid, prepared by the condensation of bromamine acid and 5-amino-4-methoxybenzyl alcohol [the latter compound may be produced by the process described in Ber. 34, 2459 (1901)], 11.0 parts potassium cyanide and 500 parts water. The contents of the autoclave were then heated at 140 C. for eight hours. The reaction mixture was then filtered, thoroughly washed with hot water until the filtrate was colorless, and dried. The final weight of the dried blue powder obtained was 12.3 parts. It dyed rayon acetate in bright blue shades which became green when exposed to the action of gas combustion fumes. The structure is shown below.

(fHzOH I l O NH Example 2 The same procedure as outlined in Example 1 was used except that the 20.0 parts of 1-amino-4-(a-hydroxy-6- methoxy-m-toluidino)-2-anthraquinonesulfonic acid were replaced by 20.0 parts of l-amino-4[u(2-hydroxyethyl)- 6-methoxy-m-toluidino] 2 anthraquinone sulfonic acid. The product possessed properties similar to those indicated in Example 1. The structure is shown below.

0 NHz ([JHaOCHaCHaOH I Example 3 Into a reaction vessel equipped with a stirrer, thermometer and reflux condenser were charged 10.0 parts N (2 hydroxyethyl) 1 (2 hydroxyethylamino)- 4 bromo 2 anthraquinonecarboxamide, 7.5 parts 5- amino-4-methoxybenzyl alcohol, 5.0 parts sodium carbonate, 5.0 parts sodium bicarbonate, 0.5 part cuprous chloride, 150 parts water and 25 parts ethanol. The resulting mixture was heated at reflux for eight hours.

It was then cooled, filtered, and washed with 200 parts hot water (65 C.). Upon drying, 7.4 parts of product were obtained which dyed cellulose acetate a bright bluegreen shade, which when exposed to the action of combustion gas fumes became bright green. The structure is shown below: i

| O NH Example 4 The same procedure as outlined in Example 3 was used except that 8 parts of 5-amino-4-methoxybenzyl-(2-hydroxy)ethyl ether were used in place of the 7.5 parts 5- amino-4-methoxybenzyl alcohol. The product possessed very similar properties to those indicated in Example 3. The structure is indicated below.

(11120 CHZCHQOH O NH Example 5 Equal amounts of the product from Example 1 and 1 amino 4-cyclohexylamino 2 anthraquinonecarboxamide were intimately mixed and the resulting mixture was dispersed in the usual manner. The resulting dyestufi mixture dyed cellulose acetate in blue shades which upon exposure to the action of combustion gas fumes dulled slightly but remained practically the same shade.

Example 6 In Example 5 above the 1-amino-4-cyclohexylamino-2- anthraquinonecarboxamide was replaced by an equal weight of 4,8-dimenthylaminoanthrarufin. In this case also, the gas fastness of the resulting mixture was much improved over the gas fastness of the two components 'when they were dyed separately.

Example 7 In Example 5 above, the 1-amino-4-cyclohexylamino Z-anthraquinonecarboxamide was replaced by an equal weight of 1-amino-2-cyano-4-(p-methylaminoanilino) anthraquinone. The gas fastness of the resulting mixture is improved in similar manner.

This invention has been described with respect to several preferred embodiments thereof and various modifications and variations thereof will become obvious to the person skilled in the art. It is to be understood that such modifications and variations are included within the spirit and purview of this application and the scope of the appended claims.

This application is a division of my application Serial No. 447,886, filed August 4, 1954, now US. Patent No. 2,768,183.

I claim:

1. A composition comprising at least one blue anthraquinone dyestufi subject to changing to reddish hues upon exposure to acid gas fumes and a blue anthraquinone dyestuff subject to changing to greenish hues upon exposure to acid gas fumes.

2. A dyestuff composition comprising 25 to 75 parts by weight of at least one blue anthraquinone dyestuff subject to changing to reddish hues upon exposure to acid gas fumes and about 75 to 25 parts by weight of a blue anthraquinone dyestuif subject to changing to greenish hues upon exposure to acid gas fumes.

3. A dyestuif composition comprising at least one blue anthraquinone dyestufi subject to changing to reddish hues upon exposure to acid gas fumes and a blue anthraquinone dyestufi of the formula wherein Y is selected from the group consisting of --CN and -CONH(RO),,X, R is lower alkyl, X is selected from the group consisting of H and lower alkyl, and n has a value of zero to 3.

5. A dyestufi composition comprising 25 to 75 parts by weight of at least one blue anthraquinone dyestufi subject to changing to reddish hues upon exposure to acid gas fumes and about 75 to 25 parts by Weight of a blue 'anthraquinone dyestufl of the formula OHaOH O NH 6. A dyestufi composition comprising 25 to 75 parts by weight of at least one blue anthraquinone dyestufi sub ject to changing to reddish hues upon exposure to acid gas fumes and about 75 to 25 parts by weight of a blue anthraquinone dyestufi of the formula CHzOCHgCHgOH 7. A dyestuif composition comprising 25 to 75 parts by weight of at least one blue anthraquinone dyestufi 70 subject to changing to reddish hues upon exposure to acid 6 gas fumes and about to 25 parts by weight of a blue anthraquinone dyestulf of the formula (III) IIIHCH2CH2OH ("3NHOH2GH2OH O (IJH2OH I I O 8. A dyestuflf composition comprising 25 to 75 parts by weight of at least one blue anthraquinone dyestuff sub ject to changing to reddish hues upon exposure to acid gas fumes and about 75 to 25 parts by weight of a blue anthraquinone dyestuif of the formula CHaO OHaCHnOH 9. A blue dyestufi composition comprising 1-ann'no-4- cyclohexylamino 2 anthraquinonecarboxamide and a compound of the formula CHzOH CH: 10. A blue dyestufi composition comprising 4,8-dimethylaminoanthrarufin and a compound of the formula CHaOH CH3 11. A blue dyestuflt' composition comprising l-amino-Z- cyano-4-(paramethylaminoanilino)anthraquinone and a compound of the formula 0 NH: H

References Cited in the file of this patent I UNITED STATES PATENTS 1,814,344 Snelling July 14, 1931 2,136,782 Bucy Nov. 15 1938 2,546,168 Hart Mam. 27, 1951 2,701,802 Boyd Feb. 8, 1955 2,768,183 Hoefle Oct. 23, 1956 

1. A COMPOSITION COMPRISING AT LEAST ONE BLUE ANTHRAQUINONE DYESTUFF SUBJECT OT CHANGING TO REDDISH HUES UPON EXPOSURE TO ACID GAS FUMES AND A BLUE ANTHRAQUINONE DYESTUFF SUBJECT TO CHANGIN TO GREENISH HUES UPON EXPOSURE TO ACID GAS FUMES. 